22666-07-5Relevant articles and documents
A mild copper-mediated Glaser-type coupling reaction under the novel CuI/NBS/DIPEA promoting system
Li, Lingjun,Wang, Jiuxia,Zhang, Guisheng,Liu, Qingfeng
, p. 4033 - 4036 (2009)
A simple copper promoting system CuI/NBS/DIPEA was first found to efficiently promote Glaser coupling reaction under ambient temperature. The alkynes with sensitive groups such as acetal and ketal, TBDMS, ester and amide could react smoothly to afford the
Application of iodanes to the dimerization of terminal alkynes
Yan, Jie,Lin, Feng,Yang, Zhenping
, p. 1301 - 1303 (2007)
The dimerization of terminal acetylenes was studied using iodanes as oxidants under palladium-catalyzed conditions. It was found that a number of iodanes were useful in the reaction, with (diacetoxyiodo)benzene and iodosylbenzene being the best oxidants.
Formation of Dimeric Acetylenes: an Unexpected Reaction of Acetylenic Selenides
Comasseto, Joao V.,Catani, Valdomiro,Ferreira, Jose T. B.,Braga, Antonio L.
, p. 1067 (1986)
1-Selenoalk-1-ynes react with m-chloroperbenzoic acid in tetrahydrofuran- water furnishing 1,4-disubstituted 1,3-diynes free of selenium in high yield.
Cu(II)-CMC: A mild, efficient and recyclable catalyst for the oxidative alkyne homocoupling reaction
Jiang, Yuqin,Guo, Niu,Li, Xiyong,Sun, Yamin,Zhang, Weiwei
, p. 549 - 554 (2017)
Cu(II) heterogenized on sodium carboxymethyl cellulose (Na-CMC) has been thoroughly characterized by different techniques. Cu(II)-CMC has been applied for the first time in the homocoupling reaction of a variety of terminal alkynes. The catalyst furnished
First example of transition-metal-free Glaser-type coupling reaction
Yan, Jincan,Wang, Lei
, p. 2333 - 2338 (2005)
In the presence of potassium tert-butoxide and in toluene, 1,1-dibromo-1-alkenes smoothly generated the corresponding Glaser-type coupling-reaction products (1,3-diynes) in moderate to good yields. Copyright Taylor & Francis, Inc.
Ligand-free copper-catalyzed synthesis of symmetrical diynes from 1,1-dibromo-1-alkenes
Jin, Hui,Kuang, Chunxiang
, p. 592 - 594 (2011)
Symmetrical diynes were synthesized by ligand-free copper-catalyzed homocoupling reaction of 1,1-dibromo-1-alkenes using a DBU/DMSO system at room temperature in good to excellent yields.
Nickel-Copper-Catalyzed C(sp2)- N Cross-Coupling of Cyclic and Bridged Amides: An Access to Cyclic Enamides and Alkenyl Vince Lactams
Maity, Pintu,Kundu, Debasish,Ranu, Brindaban C.
, p. 3617 - 3626 (2015)
An efficient C(sp2)- N cross-coupling of styrenyl and vinyl halides with cyclic and bridged amides catalyzed by nickel acetonylacetonate [Ni(acac)2] and copper(I) iodide (CuI) in the absence of any ligand has been developed. The reaction conditions are optimized to give the maximum yield of products using cesium carbonate (Cs2CO3) (2.0 equiv.) in N-methyl-2-pyrrolidinone (NMP) at 110 C under argon in the presence of Ni(acac)2/CuI (10 mol% each). A series of alkenyl derivatives of Vince lactams (bridged amides) and cyclic amides are obtained by this procedure. Halogen-containing styrenyl bromides also underwent coupling with amides to provide the products. The coupling is highly chemoselective as during the reactions the halogens (Br, Cl, F) on the aromatic ring remained intact and these can be used for further functionalization to make these enamides more useful. Although the (E)-styrenyl halides produced the corresponding (E)-styrenyl enamides, reactions with (Z)-styrenyl halides produced 1,3-di-ynes instead of (Z)-styrenyl enamides. This may be explained by the possibility of E2 type elimination of (Z)-styrenyl halides in the presence of a strong base like cesium carbonate followed by homocoupling. This catalyst system works efficiently for the N-arylation too along with N-styrenylation and vinylation. The bridged as well as cyclic amides successfully coupled with substituted aryl halides to provide the corresponding products. In general, the reactions are clean and high yielding. The operations are very simple and the products are obtained pure by standard column chromatography. The reaction is compatible with variety of amides and alkenyl bromides. The roles of nickel acetonylacetonate and copper(I) iodide in this reaction have been established and a possible reaction pathway has been outlined. The significant feature of this protocol is the alkenylation of Vince lactams via C(sp2)- N cross-coupling, which has not been reported so far and these products may have much potential in the pharmaceutical industry.
Mesoporous silica-supported copper-catalysts for homocoupling reaction of terminal alkynes at room-temperature
Li, Hongling,Yang, Min,Zhang, Xia,Yan, Liang,Li, Jing,Qi, Yanxing
, p. 1343 - 1349 (2013)
Amine-functionalized mesoporous silica-supported copper catalysts SBA-15@amine-Cu and SBA-15@Oamine-Cu were prepared and proved to be efficient and reusable for homocoupling of terminal alkynes at room temperature with air as the oxidant. SBA-15@amine-Cu exhibited better recyclability than SBA-15@Oamine-Cu. The differences in the catalytic performances of the catalysts could be ascribed to catalyst structure and the interaction between copper and the supports. The as-prepared catalysts were systematically characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES), high resolution-transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and nitrogen physical adsorption. The analysis indicated that the mesoporous structure of the materials was retained during the immobilization process. XPS results suggested that the as-prepared catalysts were not obtained by a simple physical adsorption of CuCl on the supports. It is noted that, for aliphatic alkynes, the catalytic activity of SBA-15@amine-Cu is even higher than that of the homogeneous copper catalytic system and that of some previously reported heterogeneous systems.
Palladium-catalysed coupling of 4-halopyrrolo[2,3-d]pyrimidines with arylacetylenes: Synthesis of a new heterocyclic system - 4H-pyrrolo[2,3,4-de] pyrimido[5′,4′:5,6][1,3]diazepino[1,7-a]indole
Tumkevicius, Sigitas,Masevicius, Viktoras
, p. 2327 - 2330 (2004)
Palladium-catalysed reaction of methyl 5-amino-4-chloro(or iodo)-7-methyl-2-methylthiopyrrolo[2,3-d]pyrimidine-6-carboxylate with arylacetylenes affords the corresponding 4-(arylethynyl)pyrrolopyrimidines. Reaction of 5-amino-4-iodopyrrolopyrimidine with
Cu-Catalyzed solvent-free, pot-economic synthesis of 1,3-dynes from 1,1-dibromoalkenes in the presence of DBU?H2O
Moodapelly, Shiva Krishna,Nanaji, Yerramsetti,Sharma, Gangavaram V.M.,Suneeel, Kanaparthy,Doddi, Venkata Ramana
, (2021/05/27)
An efficient synthesis of 1,3-diynes directly from 1,1-dibromoalkenes has been achieved by utilizing hydrated 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU.H2O) as a sole reagent and a catalyst CuI. In general, 1,3-diynes were synthesized from corresponding terminal alkynes, which in turn were obtained from 1,1-dibromoalkenes. The DBU.H2O allowed the synthesis of 1,3-diynes not only in a pot-efficient manner but also under solvent-free conditions at ambient temperature. A plausible mechanism is proposed via 1-bromoalkynes intermediate instead of terminal alkynes.
Method for preparing conjugated diyne compound by using copper complex
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Paragraph 0053-0058; 0059-0060; 0065-0066; ..., (2021/07/14)
The invention relates to a method for preparing a conjugated diyne compound by using a copper complex. The method comprises the following step of: in the presence of alkali, carrying out a Glaser coupling reaction at room temperature by using alkyne as a raw material, the copper complex containing ortho-carborane Schiff base ligand as a catalyst and air as an oxidizing agent to prepare the conjugated diyne compound. Compared with the prior art, the copper complex containing the ortho-carborane Schiff base ligand is used for efficiently catalyzing the Glaser coupling reaction of alkyne to prepare the conjugated diyne compound; and the method has the advantages that selectivity is good, a catalyst dosage is low, reaction conditions are mild, a reaction can be performed in an open manner (wherein air is used as an oxidizing agent), a reaction rate is high, yield is relatively high, a substrate range is wide, and the method has wide application prospects in industry.
In Situ Synthesis of CuN4/Mesoporous N-Doped Carbon for Selective Oxidative Crosscoupling of Terminal Alkynes under Mild Conditions
Cao, Yue,Gu, Dong,Lei, Aiwen,Liang, Zhenjin,Su, Yaqiong,Wu, Jinsong,Wu, Yong,Xiao, Wei,Yang, Dali,Yu, Ruohan,Zhang, Dongchao,Zhang, Yuanteng
, (2021/12/23)
The 1,3-conjugated diynes are an important class of chemical intermediates, and the selective crosscoupling of terminal alkynes is an efficient chemical process for manufacturing asymmetrical 1,3-conjugated diynes. However, it often occurs in homogenous conditions and costs a lot for reaction treatment. Herein, a copper catalyzed strategy is used to synthesize highly ordered mesoporous nitrogen-doped carbon material (OMNC), and the copper species is in situ transformed into the copper single-atom site with four nitrogen coordination (CuN4). These features make the CuN4/OMNC catalyst efficient for selective oxidative crosscoupling of terminal alkynes, and a wide range of asymmetrical and symmetrical 1,3-diynes (26 examples) under mild conditions (40?°C) and low substrates ratio (1.3). Density functional theory (DFT) calculations reveal that the aryl–alkyl crosscoupling has the lowest energy barrier on the CuN4 site, which can explain the high selectivity. In addition, the catalyst can be separated and reused by simply centrifugation or filtration. This work can open a facile avenue for constructing single-atom loaded mesoporous materials to bridge homogeneous and heterogeneous catalysis.
